Cyclic Aminophosphenium Mono‐ and Dications

Starting from the biradicaloid [ · P(μ‐NTer) 2 P·] (Ter = 2,6‐dimesitylphenyl), the addition of ethyl bromide yields the addition product [Et–P(μ‐NTer) 2 P–Br]. Using 1,6‐dibromohexane, the corresponding hexyl‐bridged species [Br–P(μ‐NTer) 2 P–hexyl–P(μ‐NTer) 2 P–Br] is formed. The addition of one or two equivalents of a strong Lewis acid such as GaCl 3 leads to the abstraction of the bromide, forming the monocation [Et–P(μ‐NTer) 2 P] + or the dication [P(μ‐NTer) 2 P–hexyl–P(μ‐NTer) 2 P] 2+ , respectively. Both new salts with the cyclic aminophosphenium cations are fully characterized, and their structure and bonding are discussed.